Lateral α-substituted acrylate compound and polymer thereof

ABSTRACT

The invention relates to compounds represented by Formula (1): 
                         
wherein R a  is alkyl or the like; R b  is fluorine or —CF 3 ; A is 1,4-cyclohexylene, 1,4-phenylene or the like; Z is a single bond, alkylene or the like; Y is a single bond, alkylene or the like; and m and n are an integer of approximately 0 to approximately 5.

CROSS REFERENCE TO RELATED APPLICATIONS

This application claims priority under 35 U.S.C. §119 to Japanese PatentApplication No. JP 2005-355180, filed Dec. 8, 2005, which application isexpressly incorporated herein by reference in its entirety.

BACKGROUND OF THE INVENTION

1. Field of the Invention

The invention relates to a compound in which a chain group havingα-substituted acryloyloxy is substituted on a 1,4-phenylene ring, acomposition containing the compound, a polymer of the compound andapplications thereof.

2. Description of the Related Art

A polymer in which a molecular configuration is fixed is obtained byaligning the molecules of a polymerizable compound having a liquidcrystallinity in a fixed direction and photopolymerizing it. It is knownthat such polymer has an optical anisotropy (see, e.g., JP H8-3111A/1996). The polymerizable compound having a liquid crystallinityincludes, for example, the acrylates shown below (see, e.g., JPH7-17910A/1995 and JP H7-316032A/1997). These acrylates have a highreactivity and provide polymers having a high transparency, but they arefurther required to be improved in characteristics such as a heatresistance and a mechanical strength.

SUMMARY OF THE INVENTION

The invention relates to a compound represented by Formula (1):

wherein in Formula (1), R^(a) is independently hydrogen, halogen, cyano,—CF₃, —CF₂H, —CFH₂, —OCF₃, —OCF₂H, —N═C═O, —N═C═S or alkyl having acarbon number of approximately 1 to approximately 20; in the alkyl,optional —CH₂— may be substituted with —O—, —S—, —SO₂—, —CO—, —COO—,—OCO—, —CH═CH—, —CF═CF— or —C≡C—, and optional hydrogen may besubstituted with halogen; R^(b) is fluorine or —CF₃; A is independently1,4-cyclohexylene, 1,4-cyclohexenylene, 1,4-phenylene,naphthalene-2,6-diyl, tetrahydronaphthalene-2,6-diyl, fluorene-2,7-diylor bicyclo[2.2.2]octane-1,4-diyl; in these rings, optional —CH₂— may besubstituted with —O—, optional —CH═ may be substituted with —N═, andoptional hydrogen may be substituted with halogen, alkyl having a carbonnumber of approximately 1 to approximately 5 or halogenated alkyl havinga carbon number of approximately 1 to approximately 5; Z isindependently a single bond or alkylene having a carbon number ofapproximately 1 to approximately 20; in the alkylene, optional —CH₂— maybe substituted with —O—, —CO—, —COO—, —OCO—, —CH═CH—, —CF═CF— or —C≡C—,and optional hydrogen may be substituted with halogen; Y is a singlebond or alkylene having a carbon number of approximately 1 toapproximately 20; in the alkylene, optional —CH₂— may be substitutedwith —O—, —CO—, —COO—, —OCO— or —CH═CH—, and optional hydrogen may besubstituted with halogen; and m and n each are an integer ofapproximately 0 to approximately 5.

DETAILED DESCRIPTION OF THE INVENTION

Reference will now be made in detail to the preferred embodiments of theinvention. This invention may, however, be embodied in many differentforms and should not be construed as limited to the embodiments setforth herein. In addition and as will be appreciated by one of skill inthe art, the invention may be embodied as a method, system or process.

The embodiments of the invention are described in the following items.The preferred examples of an end group, a ring and a bonding group inthe compound (1) shall be described below as well.

[1] A compound represented by Formula (1):

In Formula (1), R^(a) is independently hydrogen, halogen, cyano, —CF₃,—CF₂H, —CFH₂, —OCF₃, —OCF₂H, —N═C═O, —N═C═S or alkyl having a carbonnumber of approximately 1 to approximately 20; in the alkyl, optional—CH₂— may be substituted with —O—, —S—, —SO₂—, —CO—, —COO—, —OCO—,—CH═CH—, —CF═CF— or —C≡C—, and optional hydrogen may be substituted withhalogen; R^(b) is fluorine or —CF₃; A is independently1,4-cyclohexylene, 1,4-cyclohexenylene, 1,4-phenylene,naphthalene-2,6-diyl, tetrahydronaphthalene-2,6-diyl, fluorene-2,7-diylor bicyclo[2.2.2]octane-1,4-diyl; in these rings, optional —CH₂— may besubstituted with —O—, optional —CH═ may be substituted with —N═, andoptional hydrogen may be substituted with halogen, alkyl having a carbonnumber of approximately 1 to approximately 5 or halogenated alkyl havinga carbon number of approximately 1 to approximately 5; Z isindependently a single bond or alkylene having a carbon number ofapproximately 1 to approximately 20; in the alkylene, optional —CH₂— maybe substituted with —O—, —CO—, —COO—, —OCO—, —CH═CH—, —CF═CF— or —C≡C—,and optional hydrogen may be substituted with halogen; Y is a singlebond or alkylene having a carbon number of approximately 1 toapproximately 20; in the alkylene, optional —CH₂— may be substitutedwith —O—, —CO—, —COO—, —OCO— or —CH═CH—, and optional hydrogen may besubstituted with halogen; and m and n each are an integer ofapproximately 0 to approximately 5.

Preferred R^(a) are hydrogen, chlorine, fluorine, cyano, —N═C═O, —N═C═S,alkyl, alkoxy, alkoxyalkyl, alkoxyalkoxy, alkylthio, alkylthioalkoxy,alkenyl, alkenyloxy, alkenyloxyalkyl, alkoxyalkenyl, alkynyl andalkynyloxy. In the above groups, groups in which at least one hydrogenis substituted with halogen are preferred as well. Preferred halogen arefluorine and chlorine, and further preferred halogen is fluorine. Thespecific examples thereof are monofluoroalkyl, polyfluoroalkyl,perfluoroalkyl, monofluoroalkoxy, polyfluoroalkoxy and perfluoroalkoxy.In the above groups, the linear groups are preferred to the branchedgroup. Branched R^(a) is preferred for obtaining an optically activecompound.

Further preferred R^(a) are hydrogen, fluorine, chlorine, cyano, —CF₃,—CF₂H, —CFH₂, —OCF₃, —OCF₂H, alkyl having a carbon number ofapproximately 1 to approximately 10, alkoxy having a carbon number ofapproximately 1 to approximately 10 and alkoxyalkyl having a carbonnumber of approximately 2 to approximately 10. The alkyl, the alkoxy andthe alkoxyalkyl include, for example, methyl, ethyl, propyl, butyl,pentyl, hexyl, heptyl, octyl, nonyl, decyl, methoxy, ethoxy, propyloxy,butyloxy, pentyloxy, hexyloxy, heptyloxy, octyloxy, nonyloxy, decyloxy,methoxymethyl and methoxyethyl. Particularly preferred R^(a) are alkylhaving a carbon number of approximately 1 to approximately 10 and alkoxyhaving a carbon number of approximately 1 to approximately 10.

Preferred A are 1,4-cyclohexylene, 1,4-cyclohexenylene,2,2-difluoro-1,4-cyclohexylene, 1,3-dioxane-2,5-diyl, 1,4-phenylene,2-fluoro-1,4-phenylene, 2,3-difluoro-1,4-phenylene,2,5-difluoro-1,4-phenylene, 2,6-difluoro-1,4-phenylene,2,3,5-trifluoro-1,4-phenylene, pyridine-2,5-diyl,3-fluoropyridine-2,5-diyl, pyrimidine-2,5-diyl, pyridazine-3,6-diyl,naphthalene-2,6-diyl, tetrahydronaphthalene-2,6-diyl, fluorene-2,7-diyl,9-methyl-fluorene-2,7-diyl, 9,9-dimethylfluorene-2,7-diyl,9-ethylfluorene-2,7-diyl, 9-fluorofluorene-2,7-diyl and9,9-difluorofluorene-2,7-diyl.

In the configuration of 1,4-cyclohexylene and 1,3-dioxane-2,5-diyl,trans is preferred to cis. 2-Fluoro-1,4-phenylene is structurally thesame as 3-fluoro-1,4-phenylene, and therefore the latter is not given asthe example. This rule shall be applied to the relation of2,5-difluoro-1,4-phenylene to 3,6-difluoro-1,4-phenylene. When m is aninteger of approximately 2 to approximately 10, two A's optionallyselected may be the same or different.

Further preferred A are 1,4-cyclohexylene, 1,4-cyclohexenylene,1,3-dioxane-2,5-diyl, 1,4-phenylene, 2-fluoro-1,4-phenylene,2,3-difluoro-1,4-phenylene, 2,5-difluoro-1,4-phenylene and2,6-difluoro-1,4-phenylene. Particularly preferred A are1,4-cyclohexylene and 1,4-phenylene.

Preferred Z are a single bond, —(CH₂)₂—, —(CF₂)₂—, —CH₂O—, —OCH₂—,—CF₂O—, —OCF₂—, —COO—, —OCO—, —CH═CH—, —CF═CF—, —C≡C—, —(CH₂)₄—,—(CH₂)₃O—, —O(CH₂)₃—, —(CH₂)₂COO—, —OCO(CH₂)₂—, —CH═CH—COO— and—OCO—CH═CH—.

Further preferred Z are a single bond, —(CH₂)₂—, —COO—, —OCO—, —CH₂O—,—OCH₂—, —CF₂O—, —OCF₂—, —CH═CH—, —C≡C—, —(CH₂)₂COO—, —OCO(CH₂)₂—,—CH═CH—COO— and —OCO—CH═CH—. Particularly preferred Z are a single bond,—COO—, —OCO—, —CH═CH—, —(CH₂)₂COO—, —OCO(CH₂)₂—, —CH═CH—COO— and—OCO—CH═CH—. When m is an integer of approximately 2 to approximately10, two Z's optionally selected may be the same or different.

Preferred Y are a single bond and alkylene having a carbon number ofapproximately 1 to approximately 10, and in the alkylene, optional —CH₂—may be substituted with —O—, —COO— or —OCO—.

[2] The compound as described in item [1], wherein in Formula (1), m+nis an integer of approximately 1 to approximately 3.

[3] The compound as described in item [1], wherein in Formula (1), m+nis 2.

[4] The compound as described in any of the items [1] to [3], wherein inFormula (1), R^(a) is independently alkyl having a carbon number ofapproximately 1 to approximately 10, alkoxy having a carbon number ofapproximately 1 to approximately 10 or alkenyl having a carbon number ofapproximately 2 to approximately 10, and optional hydrogens thereof maybe substituted with fluorine; A is independently 1,4-cyclohexylene,1,4-phenylene, pyridine-2,5-diyl, pyridazine-3,6-diyl orpyrimidine-2,5-diyl, and optional hydrogens thereof may be substitutedwith chlorine, fluorine, alkyl having a carbon number of approximately 1to approximately 3 or fluoroalkyl having a carbon number ofapproximately 1 to 3 approximately; Z is independently a single bond,—CH₂O—, —OCH₂—, —COO—, —OCO—, —CH═CH—, —(CH₂)₂COO—, —OCO(CH₂)₂—,—CH═CH—COO—, —OCO—CH═CH— or —C≡C—; Y is a single bond or alkylene havinga carbon number of 1 to 10; in the alkylene, optional —CH₂— may besubstituted with —O—, —COO— or —OCO—.

[5] A compound represented by any of Formulas (I), (II) and (III):

In Formulas (I), (II) and (III), R^(a) is independently hydrogen,halogen, cyano, —CF₃, —CF₂H, —CFH₂, —OCF₃, —OCF₂H, —N═C═O, —N═C═S oralkyl having a carbon number of 1 to 20; in the alkyl, optional —CH₂—may be substituted with —O—, —S—, —SO₂—, —CO—, —COO—, —OCO—, —CH═CH—,CF═CF— or —C≡C—, and optional hydrogen may be substituted with halogen;R^(b) is fluorine or —CF₃; A is independently 1,4-cyclohexylene,1,4-cyclohexenylene, 1,4-phenylene, naphthalene-2,6-diyl,tetrahydronaphthalene-2,6-diyl, fluorene-2,7-diyl orbicyclo[2.2.2]octane-1,4-diyl; in these rings, optional —CH₂— may besubstituted with —O—, optional —CH═ may be substituted with —N═, andoptional hydrogen may be substituted with halogen, alkyl having a carbonnumber of approximately 1 to approximately 5 or halogenated alkyl havinga carbon number of approximately 1 to approximately 5; Z isindependently a single bond or alkylene having a carbon number ofapproximately 1 to approximately 20; in the above alkylene, optional—CH₂— may be substituted with —O—, —CO—, —COO—, —OCO—, —CH═CH—, —CF═CF—or —C≡C—, and optional hydrogen may be substituted with halogen; Y is asingle bond or alkylene having a carbon number of approximately 1 toapproximately 20; in the alkylene, optional —CH₂— may be substitutedwith —O—, —CO—, —COO—, —OCO— or —CH═CH—, and optional hydrogen may besubstituted with halogen.

[6] The compound as described in item [5], wherein in Formulas (I), (II)and (III), R^(a) is independently alkyl having a carbon number ofapproximately 1 to approximately 10, alkoxy having a carbon number ofapproximately 1 to approximately 10 or alkenyl having a carbon number ofapproximately 2 to approximately 10, and optional hydrogens thereof maybe substituted with fluorine; A is independently 1,4-cyclohexylene,1,4-phenylene, pyridine-2,5-diyl, pyridazine-3,6-diyl orpyrimidine-2,5-diyl, and optional hydrogens thereof may be substitutedwith chlorine, fluorine, alkyl having a carbon number of approximately 1to approximately 3 or fluoroalkyl having a carbon number ofapproximately 1 to approximately 3; Z is independently a single bond,—CH₂O—, —OCH₂—, —COO—, —OCO—, —CH═CH—, —(CH₂)₂COO—, —OCO(CH₂)₂—,—CH═CH—COO—, —OCO—CH═CH— or —C≡C—; Y is a single bond or alkylene havinga carbon number of approximately 1 to approximately 10; in the alkylene,optional —CH₂— may be substituted with —O—, —COO— or —OCO—.

[7] The compound as described in item [5], wherein in Formulas (I), (II)and (III), R^(a) is independently alkyl having a carbon number ofapproximately 1 to approximately 10 or alkoxy having a carbon number ofapproximately 1 to approximately 10; A is independently1,4-cyclohexylene or 1,4-phenylene; Z is independently a single bond,—COO—, —OCO—, —CH═CH—, —(CH₂)₂COO—, —OCO(CH₂)₂—, —CH═CH—COO—,—OCO—CH═CH— or —C≡C—; Y is a single bond or alkylene having a carbonnumber of approximately 1 to approximately 10; in the alkylene,—CH₂-adjacent to the ring may be substituted with —O—, —COO— or —OCO—.

[8] A composition that includes at least one compound as described inany of items [1] to [7].

[9] The composition as described in item [8], further including apolymerizable compound which is different from the compound as describedin any of items [1] to [7].

[10] The composition as described in item [8] or [9], further includinga polymerizable optically active compound which is different from thecompound as described in any of items [1] to [7].

[11] The composition as described in any of items [8] to [10], furtherincluding a non-polymerizable liquid crystalline compound.

[12] The composition as described in any of items [8] to [11], furtherincluding a non-polymerizable optically active compound.

[13] The composition as described in any of items [8] to [12], furtherincluding a polymerization initiator.

[14] The composition as described in any of items [8] to [13], furtherincluding a solvent.

[15] A polymer obtained by polymerizing the composition as described inany of items [8] to [14].

[16] The polymer as described in item [15], wherein the weight averagemolecular weight is approximately 500 to approximately 1,000,000.

[17] The polymer as described in item [15], wherein the weight averagemolecular weight is approximately 1,000 to approximately 500,000.

[18] The polymer as described in any of items [15] to [17], wherein itis an optically active compound.

[19] A film that includes the polymer as described in any of items [15]to [18].

[20] A molded article having an optical anisotropy which includes thepolymer as described in any of items [15] to [18].

[21] A liquid crystal display element that includes the composition asdescribed in any of items [8] to [14], the polymer as described in anyof items [15] to [18], the film as described in item [19] or the moldedarticle having an optical anisotropy as described in item [20].

The compound of the invention has properties such as a highpolymerization reactivity, a broad temperature range in a liquid crystalphase and a good miscibility, and the composition that includes thecompound of the invention has a good coating property and the like. Thepolymer obtained by polymerizing the composition of the invention isexcellent in characteristics such as an optical anisotropy, atransparency, a chemical stability, a heat resistance, a hardness, anadhesiveness, a firm adhesion and a mechanical strength, and it has thecharacteristic that a water permeating property, a water absorbingproperty and a gas permeating property are low. Accordingly, the polymerof the invention is suited for use as a retardation film, a polarizingelement, a circularly polarized light element, an elliptically polarizedlight element, an anti-reflection film, a selective reflection film, acolor compensator, a viewing angle compensator and a liquid crystalalignment film. The mechanical strength described above includes aYoung's modulus, a tensile strength, a tearing strength, a flexuralstrength, a flexural elastic modulus and an impact strength.

The lateral α-substituted acrylate compound according to the invention,the composition that includes the compound, the polymer obtained fromthe composition and applications thereof shall be explained in details.

Terms in the present specification shall be used in the followingmanner:

The term “liquid crystalline compound” is a general term for compoundshaving a liquid crystal phase such as a nematic phase, a smectic phaseand the like and compounds which do not have a liquid crystal phase butare useful as components for liquid crystal compositions. The term“compound (1)” means the compound represented by Formula (1). Further,it means at least one of the compounds represented by Formula (1) in acertain case. The term “composition (1)” means a composition thatincludes at least one compound selected from the compounds (1). The term“polymer (1)” means a polymer obtained by polymerizing the composition(1). The term “(meth)acryloyloxy” means acryloyloxy or methacryloyloxy,the term “(meth)acrylate” means acrylate or methacrylate, and the term“(meth)acrylic acid” means acrylic acid or methacrylic acid.

In the chemical formulas, when one compound has plural A's, optional twoA's may be the same or different. This rule shall be applied to thecodes of Y, Z and the like. The meaning of a phrase “in the alkyl,optional —CH₂— may be substituted with —O—, —CH═CH— and the like” shallbe shown below by one example. A group in which optional —CH₂— in C₄H₉—is substituted with —O— or —CH═CH— includes, for example, C₃H₇O—,CH₃—O—(CH₂)₂—, CH₃—O—CH₂—O—, H₂C═CH—(CH₂)₃—, CH₃—CH═CH—(CH₂)₂— andCH₃—CH═CH—CH₂—O—. As described above, the term “optional” means “atleast one selected without distinction.” Considering the stability ofthe compound, CH₃—O—CH₂—O— in which oxygen is not adjacent to oxygen ispreferred to CH₃—O—O—CH₂— in which oxygen is adjacent to oxygen.

Compound

The compound (1) of the invention has, as shown in Formula (1) describedabove, α-substituted acryloyloxy which is a polymerizable group andtherefore shows characteristics such as a high polymerizationreactivity, a broad temperature range in a liquid crystal phase, asuitable optical anisotropy and a good miscibility. As shown in Formula(1) described above, R^(b) in α-substituted acryloyloxy which is apolymerizable group is fluorine or —CF₃, whereby the advantages that thecompound (1) has a good orientation and a good heat resistance and thata temperature range of a liquid crystal phase is broadened are obtainedin a certain case as compared with a case where R^(b) is hydrogen ormethyl.

When the compound (1) is mixed with other liquid crystalline compoundsand polymerizable compounds, it is readily compatible with them. Thecompound (1) is characterized by that a part thereof has a liquidcrystallinity. Further, the compound (1) is characterized by that it hasan optical activity when it has asymmetric carbon.

Suitable selection of the end groups, the rings and the bonding groupsof the compound (1) make it possible to optionally control the physicalproperties such as the optical anisotropy. The effects given to theproperties of the compound (1) by the kinds of end group R^(a), the ringA and the bonding group Z shall be explained below.

When R^(a) is linear alkyl, the temperature range of the liquid crystalphase is broad, and the viscosity thereof is low. When R^(a) is branchedalkyl, the compatibility with other liquid crystalline compounds isgood. Also when R^(a) is cyano, halogen, —CF₃ or —OCF₃, a goodtemperature range of the liquid crystal phase is shown, and suitablecompatibility is provided. Particularly when R^(a) is cyano, the largeoptical anisotropy value is provided, and when it is —F, —CF₃ or —OCF₃,the small optical anisotropy value is provided.

When the ring A is 1,4-phenylene, 1,4-phenylene in which optionalhydrogen is substituted with fluorine, pyridine-2,5-diyl,pyrimidine-2,5-diyl or pyridazine-3,6-diyl, the optical anisotropy islarge. When the ring A is 1,4-cyclohexylene, 1,4-cyclohexenylene or1,3-dioxane-2,5-diyl, the optical anisotropy is small. When at least tworings of the plural rings A are 1,4-cyclohexylene, the compound has ahigh clearing point, a small optical anisotropy and a low viscosity.When at least one ring is 1,4-phenylene, the optical anisotropy isrelatively large, and the orientational order parameter is large. Whenat least two rings are 1,4-phenylene, the compound has a large opticalanisotropy, a broad temperature range in the liquid crystal phase and ahigh clearing point.

When the bonding group Z is a single bond, —(CH₂)₂—, —CH₂O—, —OCH₂—,—CF₂O—, —OCF₂—, —CH═CH—, —CF═CF— or —(CH₂)₄—, the viscosity is low. Whenthe bonding group Z is a single bond, —(CH₂)₂—, —OCF₂—, —CF₂O—, —CH═CH—or —(CH₂)₄—, the viscosity is lower. When the bonding group Z is —CH═CH—or —CF═CF—, the temperature range in the liquid crystal phase is broad,and the elastic constant ratio is large. When the bonding group Z is—C≡C—, the optical anisotropy is large.

When the compound (1) has three or less rings, the viscosity is low, andwhen it has three or more rings, the clearing point is high. In thisspecification, a six-membered ring and the like are regarded as a ring,and a three-membered ring is not regarded as a ring.

The compound (1) may be either optically active or optically inactive.When it is optically active, the compound (1) has asymmetric carbon. Aconfiguration of asymmetric carbon may be either R or S. When it hasasymmetric carbon, it has a good compatibility.

As described above, the compound having intended physical properties canbe obtained by suitably selecting the kinds of the end groups, the ringsand the bonding groups and the number of the rings.

When the compound (1) has two or less rings and when R^(a) is —Cl, —Br,—I, —COOH, —COCl, —COBr, —CHO, —OH, —OSO₂CH₃ or —OSO₂C₆H₄CH₃-p, it isparticularly useful as a synthetic intermediate. For example, when R^(a)is —COOH, —COCl or —COBr, the compound can be derived into an estercompound by using a corresponding alcohol or phenol derivative.Similarly, when R^(a) is —Cl, —Br, —I, —OH, —OSO₂CH₃ or —OSO₂C₆H₄CH₃-p,the compound can be derived into an ether compound. Also, when R^(a) is—CHO, it can be derived into —CH═CH— by a Wittig reagent. The abovecompounds can be further derived as well into another syntheticintermediates in a range in which the α-substituted acryloyloxy groupdescribed above is allowed to be stably present by combining organicsynthetic chemical methods.

The compound (1) can be synthesized by combining organic syntheticchemical methods. Methods in which the intended end groups, rings andboding groups are introduced into a starting material are described indocuments such as Houben-Wyle, METHODS OF ORGANIC CHEMISTRY, GeorgeThieme Verlag, Stuttgart; ORGANIC SYNTHESES, John Wily & Sons, Inc.;Organic Reactions, John Wily & Sons, Inc.; COMPREHENSIVE ORGANICSYNTHESIS, Pergamon Press; and NEW EXPERIMENTAL CHEMICAL COURSE,Maruzen.

α-Substituted acrylic acid and α-substituted acrylic halide can be usedfor introducing the α-substituted acryloyloxy group described above.Synthetic methods for α-fluoroacrylic fluoride are described in J. Org.Chem., 54, 5640 (1989); Japanese Patent Application Laid-Open No.158137/1985; and Japanese Patent Application Laid-Open No. 85345/1986.Synthetic methods for α-chloroacrylic chloride are described inDE2357816, DE2350119 and DE2357677. Synthetic methods forα-trifluoromethylacrylic chloride are described in Org. Lett., 3, 2915(2001) and the like. The compound (1) can be synthesized by making useof the above compounds as the starting materials.

The synthesis of the bonding group Z shall be explained in schemes 1 to12. In these schemes, MSG¹ and MSG² are monovalent organic groups havingat least one ring. Plural MSG¹ (or MSG²) may be the same or different.Compounds (1A) to (1M) correspond to the compound (1) of the invention.These methods can be applied to the optically active compound (1) andthe optically inactive compound (1).

As shown below, arylboric acid (S1) is reacted with a compound (S2)synthesized by a publicly known method in a carbonate aqueous solutionunder the presence of a catalyst such astetrakis(triphenylphosphine)palladium, whereby a compound (1A) can besynthesized. This compound (1A) can be synthesized as well by reacting acompound (S3) synthesized by a publicly known method with n-butyllithiumand subsequently with zinc chloride and then further reacting with thecompound (S2) under the presence of a catalyst such asdichlorobis-(triphenylphosphine)palladium.

As shown below, a base such as potassium t-butoxide is added to aphosphonium salt (S5) synthesized by a publicly known method to producephosphorus ylide, and it is reacted with aldehyde (S4), whereby acompound (1B) can be synthesized. The cis body is produced depending onthe reaction conditions and the base material, and therefore the cisbody is isomerized, if necessary, to the trans body by a publicly knownmethod.

As shown below, the compound (1B) is hydrogenated in the presence of acatalyst such as palladium carbon, whereby a compound (1C) can besynthesized.

As shown below, diketone (S6) is fluorinated by sulfur tetrafluoride inthe presence of a hydrogen fluoride catalyst according to a methoddescribed in J. Am. Chem. Soc., 123, 5414 (2001), whereby a compound(1D) having —(CF₂)₂— can be synthesized.

As shown below, in the method shown in the Scheme 2, a phosphonium salt(S7) is used in place of the phosphonium salt (S5) to synthesize acompound having —(CH₂)₂—CH═CH—, and this is catalytically hydrogenated,whereby a compound (1E) can be synthesized.

As shown below, the compound (S4) is first reduced by a reducing agentsuch as sodium boron hydride to obtain a compound (S8). This compound ishalogenated by hydrobromic acid or the like to obtain a compound (S9).Then, the compound (S9) is reacted with a compound (S10) in the presenceof potassium carbonate or the like, whereby a compound (1F) can besynthesized. A compound having —CH₂O— can be synthesized as well by theabove method.

As shown below, the compound (S3) is reacted with n-butyllithium andthen with carbon dioxide to obtain carboxylic acid (11). The compound(S11) is dehydrated with phenol (S10) in the presence of DCC(1,3-dicyclohexylcarbodiimide) and DMAP (4-dimethylaminopyridine),whereby a compound (1G) having —COO— can be synthesized. A compoundhaving —OCO— can be synthesized as well by the above method. Also, (S11)is reacted with thionyl chloride or oxalyl chloride and derived into anacid chloride compound, and it is reacted with (S10) in the presence ofa base such as pyridine or triethylamine, whereby the compound (1G) canbe synthesized as well.

As shown below, the compound (S3) is first treated with n-butyllithium,and then it is reacted with tetrafluoroethylene to obtain a compound(S12). Subsequently, the compound (S2) is treated with n-butyllithiumand then reacted with the compound (S12), whereby a compound (1H) can besynthesized. The compound (1H) of a cis body can be produced as well byselecting the synthetic conditions.

As shown below, a compound (S13) is reacted with the compound (S2) inthe presence of a catalyst of dichloropalladium and copper halide,whereby a compound (1J) can be synthesized.

As shown below, the compound (S13) is first subjected to lithiation withn-butyllithium and then reacted with carbon dioxide to obtain carboxylicacid (A14). Then, the carboxylic acid (S14) is dehydrated with phenol(S10) in the presence of DCC and DMAP, whereby a compound (1K) having—C≡C—COO— can be synthesized. A compound having —OCO—C≡C— can besynthesized as well by the above method. Also, as (S11) has been derivedinto (1G) in the scheme 7, the compound (1K) can be synthesized as wellthrough an acid chloride compound.

As shown below, the compound (S13) is subjected to cross couplingreaction with vinyl bromide (S15), whereby a compound (1L) having—C≡C—CH═CH— can be synthesized. Use of the compound (S15) of a cis bodymakes it possible to produce (1L) of a cis body.

As shown below, the compound (1G) is first treated with a sulfurizingagent such as a Lawson's reagent to obtain a compound (S16). Then, ahydrogen fluoride pyridine complex and NBS (N-bromosuccinimide) are usedto fluorinate the compound (S16), whereby a compound (1M) having —CF₂O—can be synthesized. The compound (1M) can be synthesized as well byfluorinating the compound (S16) by (diethylamino)sulfur trifluoride(DAST). The compound having —OCF₂— can be synthesized as well by theabove method. It is possible as well to produce the bonding groupsthereof by a method described by P. Kirsch et al., Angew. Chem. Int.Ed., 40, 1180 (2001).

The examples (Compounds (a-1) to (d-8)) of the compounds synthesized bythe methods described above shall be shown below. The structures of thecompounds synthesized in the manners described above can be confirmedby, for example, ¹H-NMR spectrum.

Composition

The composition (1) of the invention has characteristics such as havinga good coating property and the like. The first embodiment in thecomposition (1) of the invention includes one compound (1). Ahomopolymer is obtained by polymerizing this composition. The secondembodiment includes at least two compounds selected from the compounds(1). A copolymer is obtained by polymerizing this composition. Thesecompositions may further include additives. The third embodimentincludes at least one compound (1) and other polymerizable compounds.The other polymerizable compounds are compounds having a polymerizablegroup, but they are different from the compound (1). A copolymer isobtained as well by polymerizing this composition. The composition (1)of the invention may further include additives such as liquidcrystalline compounds, optically active compounds, polymerizationinitiators, solvents, surfactants, antioxidants, UV absorbers and thelike. These additives shall be explained in order of (1) the otherpolymerizable compounds, (2) the liquid crystalline compounds, (3) theoptically active compounds, (4) the polymerization initiators, (5) thesolvents, (6) the surfactants, (7) the antioxidants and (8) the UVabsorbers.

1. Other Polymerizable Compounds

The composition (1) may include other polymerizable compounds. Compoundswhich do not reduce the coating film-producing property and themechanical strength are preferred as the other polymerizable compounds.These compounds are classified into compounds having no liquidcrystallinity and compounds having a liquid crystallinity.

The other polymerizable compounds having no liquid crystallinity includevinyl derivatives, styrene derivatives, (meth)acrylic acid derivatives,sorbic acid derivatives, fumaric acid derivatives and itaconic acidderivatives.

Preferred vinyl derivatives include, for example, vinyl chloride, vinylfluoride, vinyl acetate, vinyl pivalate, vinyl 2,2-dimethylbutanoate,vinyl 2,2-dimethylpentanoate, vinyl 2-methyl-2-butanoate, vinylpropionate, vinyl stearate, vinyl 2-ethyl-2-methyl-butanoate,N-vinylacetamide, vinyl p-t-butylbenzoate, vinylN,N-dimethylaminobenzoate, vinyl benzoate, ethyl vinyl ether,hydroxybutyl monovinyl ether, t-amyl vinyl ether,cyclohexanedimethanolmethyl vinyl ether, α,β-vinylnaphthalene, methylvinyl ketone and isobutyl vinyl ketone.

Preferred styrene derivatives include, for example, styrene,o-chlorostyrene, m-chlorostyrene, p-chlorostyrene,o-chloromethylstyrene, m-chloromethylstyrene, p-chloromethylstyrene andα-methylstyrene.

Preferred (meth)acrylic acid derivatives include, for example, methyl(meth)acrylate, ethyl(meth)acrylate, butyl(meth)acrylate,2-ethylhexyl(meth)acrylate, phenyl (meth)acrylate, 1,4-butanedioldiacrylate, 1,6-hexanediol diacrylate, 1,9-nonanediol diacrylate,neopentyl glycol diacrylate, triethylene glycol diacrylate, dipropyleneglycol diacrylate, tripropylene glycol diacrylate, tetraethylene glycoldiacrylate, trimethylolpropane triacrylate, trimethylol EO-addedtriacrylate, pentaerythritol triacrylate, trisacryloyloxyethylphosphate, bisphenol A EO-added diacrylate, bisphenol A glycidyldiacrylate (Biscoat 700® manufactured by Osaka Organic Chemical Co.,Ltd.), polyethylene glycol diacrylate and dimethyl itaconate.

Preferred sorbic acid derivatives include, for example, sodium sorbate,potassium sorbate, lithium sorbate, 1-naphthylmethylammonium sorbate,benzylammonium sorbate, dodecylammonium sorbate, octadecylammoniumsorbate, methyl sorbate, ethyl sorbate, propyl sorbate, isopropylsorbate, butyl sorbate, t-butyl sorbate, hexyl sorbate, octyl sorbate,octadecyl sorbate, cyclopentyl sorbate, cyclohexyl sorbate, vinylsorbate, allyl sorbate and propargyl sorbate.

Preferred fumaric acid derivatives include, for example, dimethylfumarate, diethyl fumarate, diisopropyl fumarate, dibutyl fumarate,dicyclopentyl fumarate and dicyclohexyl fumarate.

Preferred itaconic acid derivatives include, for example, diethylitaconate, dibutyl itaconate and diisopropyl itaconate.

In addition thereto, many polymerizable compounds such as butadiene,isoprene and maleimide can be used.

The other polymerizable compounds having a liquid crystallinity includeliquid crystalline compounds which have an acryloyloxy group, amethacryloyloxy group, a fumaroyloxy group, a maleimidyl group, anoxirane ring or an oxetane ring as a functional group and which are notthe compound (1). Such compounds can be used as well for controlling aliquid crystal phase temperature range of the composition (1). Amongthem, the liquid crystalline acrylic acid derivatives are preferredsince they provide polymers which are transparent and have a largemechanical strength. In the compound excluding the liquid crystallineacrylic acid derivatives described above, time required forpolymerization thereof is longer in a certain case than those of theacrylic acid derivatives. However, the above polymerizable compounds areuseful in the points that side products are inhibited from beingproduced and that a mechanical strength and a heat stability of thepolymers are enhanced.

In order to maintain the characteristics of the polymer of the inventionand allow the characteristics of the copolymers described above to benotably revealed, structural units derived from compounds other than thecompound (1) are desirably contained in a range of preferably fromapproximately 5 to approximately 95 mole %, and more preferably fromapproximately 60 to approximately 95 mole %. The structural unit havinga liquid crystallinity and the structural unit having no liquidcrystallinity can freely be changed in the range described above. Thetotal amount thereof may advisably fall in the range described above oreither of them may be contained.

The other polymerizable compounds having a liquid crystallinitydescribed above include, for example, compounds represented by thefollowing Formulas (BRM-1) to (BRM-16).

In Formulas (BRM-1) to (BRM-16) described above, P⁰ represents apolymerizable group including an acryloyloxy group, a methacryloyloxygroup, a fumaroyloxy group, a maleimidyl group, an oxirane ring or anoxetane ring; γ represents approximately 0 to approximately 15; δrepresents approximately 0 or approximately 1; X⁰ represents alkyl oralkoxy having a carbon number of approximately 1 to approximately 15,halogen, halogenated alkyl or alkoxy having a carbon number ofapproximately 1 to approximately 3, cyano or —O(CH₂)γP⁰; and L¹, L², L³and L⁴ represent independently hydrogen, halogen, alkyl or alkoxy havinga carbon number of approximately 1 to approximately 15 or halogenatedalkyl or alkoxy having a carbon number of approximately 1 toapproximately 3.

Among them, the particularly preferred other polymerizable compoundshaving a liquid crystallinity are shown as examples in the followingFormulas (BRM-a-1) to (BRM-a-11) and (BRM-b-1) to (BRM-b-13). Anycompounds can suitably be used as long as they are liquid crystallinecompounds having the same physical properties, and therefore the abovecompounds shown as the examples shall not restrict the structure of thecomposition of the invention.

2. Liquid Crystalline Compound

The composition (1) may contain a liquid crystalline compound having nopolymerizable group. The examples of such non-polymerizable liquidcrystalline compound are described in LiqCryst, LC I Publisher GmbH,Hamburg, Germany, which is a data base for liquid crystalline compounds.The compound (1) has characteristics such as a broad temperature rangeof a liquid crystal phase and a good compatibility with other liquidcrystalline compounds. Accordingly, the composition (1) containing theliquid crystalline compound can be used as a liquid crystal compositionfilled into a liquid crystal display element. Such composition (1) mayfurther contain additives such as a dichroic pigment and the like. Acomposite material of the polymer of the compound (1) and the liquidcrystalline compound can be obtained by polymerizing the composition (1)containing the liquid crystalline compound.

3. Optically Active Compound

The composition (1) may contain an optically active compound. Aretardation film showing a helical structure (twist structure) isobtained by coating a composition containing a suited amount of thecompound (1) having an optical activity or a composition obtained byadding a suited amount of an optically active compound to the compound(1) which is not optically active on a substrate subjected to aligningtreatment and polymerizing it. This helical structure is fixed bypolymerizing the compound (1). The characteristics of the optical isomerobtained depend on a helical pitch of the helical structure obtained.This helical pitch length can be controlled by the kind and additionamount of the optically active compound. The optically active compoundadded may be single, and plural optically active compounds may be usedfor the purpose of offsetting a temperature dependency of the helicalpitch. Polymerizable compounds other than the compound (1) in additionto the compound (1) and the optically active compound may be containedin the composition (1).

In selective reflection of visible light which is a characteristic ofthe optical isomer described above, a helical structure works onincident light to allow circularly polarized light and ellipticallypolarized light to be reflected. A selective reflection characteristicis shown by λ=n-Pitch (λ is a selective reflection central wavelength; nis an average refraction index; and Pitch is a helical pitch), andtherefore λ and a band thereof (Δλ) can suitably be controlled by n orPitch. Δλ may be advisably decreased in order to improve a color purity,and Δλ may be advisably increased when reflection in a broad band isdesired. Further, this selective reflection is influenced to a largeextent by a cell thickness. In order to maintain the color purity,attentions have to be paid so that the cell thickness is not reduced toomuch. In order to maintain homogeneity in alignment, attentions have tobe paid so that the cell thickness does not grow too large. Accordingly,the cell thickness has to be suitably controlled, and it is preferablyapproximately 0.5 to approximately 25 μm, more preferably approximately0.5 to approximately 5 μm.

A negative type c-plate described in W. H. de Jeu, PHYSICAL PROPERTIESOF LIQUID CRYSTALLINE MATERIALS, Gordon and Breach, New York (1980) canbe prepared by making a helical pitch further shorter than that ofvisible light. Shortening of the helical pitch can be achieved by usingan optically active compound having a large helical twisting power (HTP)and increasing an addition amount thereof. To be specific, the negativetype c-plate can be prepared by controlling λ to approximately 350 nm orless, preferably approximately 200 nm or less. This negative typec-plate becomes an optical compensator suited to display elements of aVAN type, a VAC type and an OCB type out of liquid crystal displayelements.

Any optically active compounds may be used for the optically activecompound described above as long as they induce a helical structure andcan suitably be mixed with the polymerizable liquid crystal compositionwhich is the base. Either of the polymerizable compound and thenon-polymerizable compound may be used, and the optimum compound can beadded according to the purposes. Considering the heat resistance and thesolvent resistance, the polymerizable compound is suited. Further, theoptically active compound having a large helical twisting power (HTP)described above is suited in terms of shortening the helical pitch. Therepresentative examples of the optically active compound having a largehelical twisting power (HTP) are disclosed in GB2298202 and DE10221751.

Optically active compounds (Op-1) to (Op-19) shown below are suited asthe optically active compound described above, and the compounds (Op-14)to (Op-19) are particularly suited. In the formulas, R^(c) representspolymerizable or non-polymerizable alkyl or alkoxy having a carbonnumber of approximately 1 to approximately 10, and a CH₃ group at thechain end may be substituted with —OCOCH═CH₂. Plural R^(c) may be thesame or different. Carbon affixed with “*” is asymmetric carbon.

4. Polymerization Initiator

The composition (1) may contain a polymerization initiator. Preferredpolymerization initiators for optical radical polymerization include,for example, 2-hydroxy-2-methyl-1-phenylpropane-1-one (trade name:Darocure 1173®), 1-hydroxycyclohexyl phenyl ketone (trade name: Irgacure184®), 2,2-dimethoxy-1,2-diphenylethane-1-one (trade name: Irgacure651®), Irgacure 500®, Irgacure 2959®, Irgacure 907®, Irgacure 369®,Irgacure 1300®, Irgacure 819®, Irgacure 1700®, Irgacure 1800®, Irgacure1850®, Darocure 4265®, Irgacure 784®,p-methoxyphenyl-2,4-bis(trichloromethyl)triazine,2-(p-butoxystyryl)-5-trichloromethyl-1,3,4-oxadiazole, 9-phenylacridine,1-(4-isopropylphenyl)-2-hydroxy-2-methylpropane-1-one, benzyl dimethylketal and a2-methyl-1-[4-(methylthio)phenyl]-2-morpholinopropane-1,2,4-diethylxanthone/methylp-dimethylaminobenzoate mixture.

Preferred polymerization initiators for thermal radical polymerizationinclude, for example, benzoyl peroxide, diisopropylperoxy dicarbonate,t-butylperoxy 2-ethylhexanoate, t-butylperoxy pivalate, di-t-butylperoxide (DTBPO), t-butylperoxy diisobutyrate, lauroyl peroxide,dimethyl 2,2′-azobisisobutyrate (MAIB), azobisisobutyronitrile (AIBN)and azobiscyclohexanecarbonitrile (ACAN).

Preferred initiators for anionic polymerization, coordinationpolymerization and living polymerization include, for example, alkalimetal alkyl such as n-C₄H₉Li and t-C₄H₉Li—R₃Al, aluminum compounds andtransition metal compounds.

5. Solvent

The composition (1) may contain a solvent. The composition (1) may bepolymerized in a solvent or in the absence of a solvent. When an alignedfilm, an anti-reflection film and a viewing angle compensator areproduced by photopolymerization, the composition (1) containing asolvent is coated on a substrate, and the solvent is removed. Then, itmay be polymerized by irradiating with light.

Preferred solvents include, for example, benzene, toluene, xylene,mesitylene, hexane, heptane, octane, nonane, decane, tetrahydrofuran,γ-butyrolactone, N-methylpyrrolidone, dimethyl formamide,dimethylsulfoxide, cyclohexane, methylcyclohexane, cyclopentanone,cyclohexanone and PGMEA. The solvent may be used alone or in a mixtureof two or more kinds thereof.

The composition can be coated on the substrate by means of a publiclyknown coater (e.g., a doctor blade, a coating apparatus and the like).It is not so meaningful to restrict a use proportion of the solvent inpolymerization. Considering the polymerization efficiency, the solventcost, the energy cost and the like, it may be determined by individualcase.

6. Surfactant

The composition (1) may contain a surfactant. The surfactant facilitatescoating of the composition on a supporting substrate and controlsalignment of the liquid crystal phase. Preferred surfactants include,for example, quaternary ammonium salts, alkylamine oxide, polyaminederivatives, polyoxyethylene-polyoxypropylene condensation products,polyethylene glycol and esters thereof, sodium laurylsulfate, ammoniumlaurylsulfate, amines laurylsulfate, alkyl-substituted aromatic sulfonicacid salts, alkylphosphoric acid salts, perfluoroalkylsulfonic acidsalts, perfluoroalkylcarboxylic acid salts, perfluoroalkyl ethyleneoxide adducts and perfluoroalkyl trimethylammonium salts. The amount ofthe surfactant is varied according to the kind of the surfactant and acomposition ratio of the composition, and it falls in a range of fromapproximately 100 ppm to approximately 5% by weight, preferably fromapproximately 0.1 to approximately 1% by weight based on the weight ofthe whole composition (1) (excluding the solvent).

7. Antioxidant

The composition (1) may contain an antioxidant. The composition (1) hasa high polymerizability, and therefore the antioxidant makes it easy tohandle. Preferred antioxidants include, for example, hydroquinone,2,6-di-t-butyl-p-cresol, 2,6-di-t-butylphenol, triphenyl phosphite andtrialkyl phosphite, and the preferred commercially available productsinclude Irganox 245® and Irganox 1035® each manufactured by CibaSpecialty Chemicals Co., Ltd.

8. UV Absorber

The composition (1) may contain a UV absorber. The composition (1) has ahigh polymerizability, and therefore the storage stability is enhancedby the UV absorber. Preferred UV absorbers include, for example, TinuvinPSI, Tinuvin 213®, Tinuvin 1090®, Tinuvin 328®, Tinuvin 384-2® andTinuvin 327® each manufactured by Ciba Specialty Chemicals Co., Ltd.

Polymer

The polymer of the invention is obtained by polymerizing the composition(1) containing at least one compound (1). This polymer shall be shown asthe polymer (1). The polymer (1) of the invention has characteristicssuch as good optical anisotropy, high transparency, good chemicalstability, good heat resistance, low water absorbing property, low gaspermeating property, good hardness and good mechanical strength. Themechanical strength described above includes a Young's modulus, atensile strength, a tearing strength, a flexural strength, a flexuralelastic modulus and an impact strength. The polymer (1) has a structuralunit derived from the compound (1).

The kind of the polymerizations include radical polymerization, anionicpolymerization, cationic polymerization and coordination polymerization.Preferred reaction temperatures fall in the range of from approximately0 to approximately 150° C., and the preferred reaction time is fromapproximately 1 to approximately 100 hours. The kind of the polymerobtained includes a homopolymer, a random copolymer, an alternatingcopolymer, a block copolymer and a graft copolymer. The polymerizationmethod and the polymer which are suited to the uses are preferablyselected.

The polymer (1) is a thermoplastic resin or a thermosetting resin. Theweight average molecular weight of the thermoplastic resin falls in therange of preferably from approximately 500 to approximately 1,000,000,more preferably from approximately 1,000 to approximately 500,000 andparticularly preferably from approximately 5,000 to approximately100,000. Such polymer (1) is soluble in a solvent, and therefore it isreadily molded into a shape suited to uses. For obtaining thethermoplastic resin, the compound (1) may be used alone or incombination with other polymerizable compounds having a polymerizablegroup at a single end. On the other hand, when a compound having apolymerizable group at both ends is used as the other polymerizablecompound, a thermosetting resin is liable to be obtained. Thethermosetting resin has a three-dimensional cross-linked structure. Suchpolymer (1) is insoluble in a solvent, and therefore the molecularweight can not be measured. When the composition of the invention iscoated on a substrate and polymerized to fix alignment of the moleculesto thereby obtain an optical anisotropy, it is not further processed, sothat the size of the molecular weight is out of the question, and theconditions may advisably be satisfied in the use environment.

A cross-linking agent may be added in order to enhance more themolecular weight. A molecular weight of the polymer obtained isinfinitely enlarged by adding the cross-linking agent, and a polymerthat exhibits excellent chemical resistance and heat resistance can beobtained. Any compounds can be used as the cross-linking agent as longas they are publicly known to persons having an ordinary skill in theart, and includes, for example, tris(3-mercaptopropionate) and the like.

The polymer (1) of the invention can be used in the forms of a film, afiber, a molded article and the like. The preferred form is a film. Thefilm is obtained by a method in which the composition (1) is coated on asubstrate and polymerized, a method in which a solution of the polymer(1) is coated on an aligned substrate and in which the solvent isremoved and a method in which the polymer (1) is subjected to pressmolding. A thickness of the polymer is varied according to a value ofthe optical anisotropy of the polymer and the uses, and therefore therange thereof can not strictly be determined. The thickness falls, forexample, in a range of from approximately 0.05 to approximately 50 μm,preferably from approximately 0.1 to approximately 20 μm and morepreferably from approximately 0.5 to approximately 10 μm.

When an optically anisotropic thin film is formed on a substrate, anysubstrates can suitably be used as long as they are publicly known topersons having an ordinary skill in the art. They include, for example,glass, polyesters such as polyethylene terephthalate (PET), polyvinylalcohol (PVA), polycarbonate (PC), triacetyl cellulose (TAC) andnorbornene base polymers. The commercially available products include,for example, Zeonoa® and Zeonex® each manufactured by Zeon Corporationand Arton® manufactured by JSR Co., Ltd. The polymer (1) of theinvention exhibits excellent adhesion to the above substrates.

The classification of alignment in the invention includes homogeneous(parallel), homeotropic (vertical), hybrid, tilt and twist. Homogeneousalignment indicates a situation in which an aligned vector is parallelto a substrate and stays in a single direction. Homeotropic alignmentindicates a situation in which an aligned vector is vertical to asubstrate. Hybrid alignment indicates a situation in which an alignedvector stands up vertically from parallel as it gets away from asubstrate. Tilt alignment indicates a situation in which an alignedvector rises up in a constant tilt angle to a substrate. Thesealignments are observed in compounds and compositions each having anematic phase and the like. On the other hand, twist alignment isobserved in compositions having a chiral nematic phase, a cholestericphase and the like. Twist alignment means a situation in which analigned vector is parallel to a substrate but twisted little by littleas it gets away from the substrate. This twist is produced by an actionof an optically active group.

The alignment of the composition (1) on the substrate can be obtained,for example, by subjecting an aligned film coated on the substrate to arubbing treatment and coating the composition (1) thereon. The purposecan be achieved even if any of aligned films publicly known to personshaving an ordinary skill in the art is used as long as the alignment canbe controlled. Polyimide, polyamide and polyvinyl alcohol base alignedfilms are suited. Further, alignment can be obtained as well by rubbingthe substrate itself with a rubbing cloth and then coating thecomposition (1) directly thereon. In the homeotropic alignment, rubbingis not necessarily required in a certain case. The aligned compositionis polymerized by irradiation with light to provide an optical isomer,and therefore it is an industrially advantageous method.

The polymer (1) is provided with an optical anisotropy by fixingmolecular arrangement. Such polymer is called an optical isomer. Whenthe compound (1) is optically active, the polymer (1) is provided with afixed helical structure. When the compound (1) is optically inactive,the polymer (1) having a fixed helical structure can be obtained byadding an optically active compound to this composition.

The polymer (1) in which both of molecular arrangement and a helicalstructure are fixed is suited to uses as, for example, a retardationfilm, a polarizing element, a circularly polarized light element, anelliptically polarized light element, an anti-reflection film, aselective reflection film, a color compensator, a viewing anglecompensator and a liquid crystal alignment film. The polymer (1) inwhich molecular arrangement is fixed is suited to uses as, for example,a retardation film, a circularly polarized light element, anelliptically polarized light element, a selective reflection film, acolor compensator and a viewing angle compensator. The polymer (1) inwhich the helical structure is fixed is suited to use as ananti-reflection film and a color compensator. The polymer (1) in whichboth of molecular arrangement and a helical structure are not fixed issuited to use as an anti-reflection film and a liquid crystal alignmentfilm. In all cases, it can be used as well for adhesives, syntheticpolymers having a mechanical anisotropy, cosmetics, ornamental articles,non-linear optical materials and information storage materials.

Heat polymerization and photopolymerization are suited for fixingmolecular arrangement and helical structure. The heat polymerization iscarried out preferably in the presence of a radical polymerizationinitiator. The photopolymerization is carried out preferably in thepresence of an optical radical polymerization initiator. For example, apolymer in which molecules are arranged in the direction of polarizationis obtained by a polymerization method in which a UV ray or an electronbeam is irradiated in the presence of an optical radical polymerizationinitiator. Such polymer can be used for a liquid crystal alignment filmwithout subjecting it to rubbing treatment.

A retardation film is obtained by polymerizing the compositioncontaining the optically active compound (1). The retardation film isobtained as well by polymerizing the composition containing theoptically inactive compound (1) and a suited amount of an opticallyactive compound. These compositions are optically active and thereforehave a helical structure. When these compositions are polymerized on asubstrate subjected to aligning treatment, polymers in which the helicalstructure and molecular arrangement are fixed are obtained. Thecharacteristics of the retardation film depend on the pitch in thehelical structure. This helical pitch can be controlled by the kind andaddition amount of the optically active compound. An addition amountthereof is usually from approximately 0.01 to approximately 50% byweight, preferably from approximately 1 to approximately 30% by weightbased on the weight of the whole composition (excluding the solvent).The optically active compound may be single, and the plural opticallyactive compounds may be added for the purpose of offsetting atemperature dependency of the helical pitch.

The polymer isolated is dissolve in a solvent and can be processed intoa film and the like. Two kinds of the polymers may be mixed andprocessed, and the polymer may be laminated. Preferred solvents include,for example, N-methyl-2-pyrrolidone, dimethylsulfoxide,N,N-dimethylacetamide, N,N-dimethylformamide, N,N-dimethylacetamidedimethylacetal, tetrahydrofuran, chloroform, 1,4-dioxane,bis(methoxyethyl)ether, γ-butyrolactone, tetramethylurea,trifluoroacetic acid, ethyl trifluoroacetate, hexafluoro-2-propanol,2-methoxyethyl acetate, methyl ethyl ketone, cyclopentanone andcyclohexanone. The above solvents may be use in a mixture withconventional organic solvents such as acetone, benzene, toluene, heptaneand methylene chloride

It will be apparent to those skilled in the art that variousmodifications and variations can be made in the invention and specificexamples provided herein without departing from the spirit or scope ofthe invention. Thus, it is intended that the invention covers themodifications and variations of this invention that come within thescope of any claims and their equivalents.

The following examples are for illustrative purposes only and are notintended, nor should they be interpreted to, limit the scope of theinvention.

EXAMPLES

The invention shall more specifically be explained below with referenceto examples, but the invention shall not be restricted by theseexamples.

The structures of the compounds were confirmed by a nuclear magneticresonance spectrum, an infrared absorption spectrum, a mass spectrum andthe like. The unit of phase transition temperature is ° C.; C representscrystal; N represents a nematic phase; and I represents an isotropicliquid phase. The measuring methods of the physical property valuesshall be shown below.

(1) Helical Pitch

The sample compound 1 part by weight was dissolved in the followingcomposition (M-1) 99 parts by weight to prepare a composition, and thehelical pitch was measured at 25° C. based on a wedge method of Cano(Applied Physics, 43, 125(1974)).

(2) Weight Average Molecular Weight and Number Average Molecular Weight

A “Shimadzu LC-9A type gel permeation chromatograph” manufactured byShimadzu Corporation and a “Column Shodex GF-7M HQ” manufactured byShowa Denko K. K. were used to measure them in DMF which was adeveloping solvent.

(3) Pencil Hardness

Pencil hardness was measured according to a JIS standard “JIS-K-5400 8.4pencil scratch test.”

(4) Other

The characteristics such as a mechanical strength and the like weremeasured based on methods described in JIS standards.

Example 1

A compound (c-1) shown below was synthesized in the following manner.

First Step

A compound (ex1-1) 25 mmol, 2-benzyloxyethanol 27 mmol and4-dimethylaminopyridine (DMAP) 7 mmol were added to 75 mL ofdichloromethane and stirred under nitrogen atmosphere. A dichloromethane25 mL solution of 1,3-dicyclohexylcarbodiimide (DCC) 27 mmol wasdropwise added thereto. After dropwise adding, the solution was stirredat room temperature for 10 hours. A precipitate deposited was filteredoff, and the organic layer was washed with water and dried on anhydrousmagnesium sulfate. The solvent was distilled off under reduced pressure,and the residue was refined by column chromatography and recrystallizedfrom ethanol, whereby a compound (ex1-2) 18 mmol was obtained.

Second Step

The compound (ex1-2) 18 mmol and 5% —Pd/C 0.5 g were added to ethylacetate and stirred at room temperature for 5 hours under hydrogenatmosphere. Pd/C was removed, and then recrystallization was carried outfrom heptane, whereby a compound (ex1-3) 15 mmol was obtained.

Third Step

An N,N-dimethylformamide (DMF) 45 mL solution of the compound (ex1-3) 15mmol was cooled to −20° C. under nitrogen atmosphere. A DMF 20 mLsolution of α-fluoroacrylic acid fluoride 45 mmol was dropwise addedthereto. The solution was stirred at room temperature for 18 hours, andwater was added thereto, followed by extracting the solution withtoluene. The organic layer was washed water and dried on anhydrousmagnesium sulfate. The solvent was distilled off under reduced pressure,and the residue was refined by column chromatography andrecrystallization from ethanol to obtain the intended compound (c-1) 11mmol.

A phase transition temperature, an NMR measuring data and a meltingpoint of the compound (c-1) are shown below.

Phase transition temperature: C 89.8 N 96.4 I; ¹H-NMR (CDCl₃): 1.00 (t,6H), 1.48 to 1.57 (m, 4H), 1.79 to 1.85 (m, 4H), 4.04 to 4.08 (m, 4H),4.26 to 4.29 (m, 2H), 4.43 to 4.46 (m, 2H), 5.33 (d, d, 1H), 5.66 (d, d,1H), 6.98 (d, 4H), 7.28 (d, 1H), 7.49 (d, d, 1H), 7.92 (d, 1H), 8.15 (d,4H); ¹⁹F-NMR (CDCl₃): -117.73 (d, d, 1F).

Example 2

A photopolymerization initiator Irgacure 907® (manufactured by CibaSpecialty Chemicals Co., Ltd.) 3 parts by weight was added to acomposition comprising the compound (c-1) 25 parts by weight produced inExample 1, 1,4-bis(4-(6-acryloyloxyhexyloxy)benzoyloxy)benzene 45 partsby weight and 4-(trans-4-propylcyclohexyl)-cyanobenzene 27 parts byweight. The above polymerizable composition 100 parts by weightcontaining the photopolymerization initiator was dissolved incyclopentanone 200 parts by weight to prepare a solution having aconcentration of approximately 33% by weight. This solution was coatedon a glass substrate having a polyimide aligned film subjected torubbing treatment by means of a bar coater while controlling so that athickness of the solution was about 12 μm. Then, this glass substratewas put on a hot plate heated at 70° C. for 120 seconds to vaporize thesolvent. Molecular alignment was expected to be fixed by the aboveoperation.

Next, the composition was irradiated with light having an intensity of30 mW/cm² (central wavelength: 365 nm) for 20 seconds under nitrogenatmosphere by means of an extra high mercury lamp of 250 W while heatingon a hot plate at 70° C. to polymerize it. A film thus obtained wasobserved under a polarizing microscope cross nicols while rotatingclockwise a polarizer and an analyzer to find that light and darknesswere turned round by every 45°, so that the homogeneous alignment wasconfirmed.

Example 3

The compound (c-1) 10 mg produced in Example 1,azobiscyclohexanecarbonitrile 0.1 mg as a polymerization initiator andbenzene 100 μL were put in an ampul of glass. This was cooled to −60° C.and sufficiently deaerated by means of a vacuum pump, and then it wassealed. This ampul was heated at 110° C. for 24 hours. The resultingreaction mixture was reprecipitated three times from 15 mL of methanolto obtain 6.8 mg of a polymer.

The polymer thus obtained had a weight average molecular weight (Mw) of25,000 measured by GPC and a dispersibility (Mw/Mn) of 2.01. The polymer1.378 mg was dipped in 1 mL of purified water and left standing at 50°C. for 10 days, and then the polymer was taken out, dried well andmeasured for a weight to find that it was 1.385 mg. It was confirmedfrom this measurement that the polymer obtained had a low waterabsorption coefficient.

Example 4

The polymer 5 parts by weight produced in Example 3 was dissolved in NMP100 parts by weight. This solution was coated on two plates of a glasssubstrate which was sufficiently washed in advance by means of a spincoater. These glass substrates were heated at 200° C. for 3 hours toremove the solvent, whereby a thin film of the polymer was formed on theglass substrate. The surfaces of the thin films of the polymer formed onthe above glass substrates were rubbed in a single direction by means ofa roller equipped with a rubbing cloth and subjected to rubbingtreatment. Two plates of the above glass substrates were stuck togethervia spacers having a thickness of 10 μm with the thin films of thepolymer being opposite to each other so that the rubbing directions werethe same, whereby a cell was prepared. A liquid crystal compositionZLI-1132® manufactured by Merck Co., Ltd. was injected into the abovecell at room temperature. The liquid crystal composition in the liquidcrystal cell showed even homogeneous alignment.

Composition Examples

The suitable examples of compositions which can be prepared using thecompounds (1) of the invention shall be shown below as CompositionExample 1 to Composition Example 6. All compositions were polymerized byirradiation with a UV ray to provide polymers having an opticalanisotropy. Percentage (%) in the following examples shows % by weight.

Composition Example 1

20%

30%

30%

20%

Composition Example 2

15%

25%

30%

30%

Composition Example 3

30%

20%

20%

30%

Composition Example 4

30%

30%

40%

Composition Example 5

10%

20%

40%

30%

Composition Example 6

35%

25%

40%

The composition of the invention has applicability as a liquid crystalcomposition for a liquid crystal display element. The polymer of theinvention has applicability to, for example, a retardation film, apolarizing element, a circularly polarized light element, anelliptically polarized light element, an anti-reflection film, aselective reflection film, a color compensator, a viewing anglecompensator, a liquid crystal alignment film and an adhesive.

1. A compound represented by Formula (1):

wherein in Formula (1), R^(a) is independently halogen, cyano, —CF₃,—CF₂H, —CFH₂, —OCF₃, —OCF₂H, —N═C═O, —N═C═S or alkyl having a carbonnumber of approximately 1 to approximately 20; in the alkyl, optional—CH₂— may be substituted with —O—, —S—, —SO₂—, —CO—, —COO—, —OCO—,—CH═CH—, —CF═CF— or —C≡C—, and optional hydrogen may be substituted withhalogen; R^(b) is fluorine or —CF₃; A is independently1,4-cyclohexylene, 1,4-cyclohexenylene, 1,4-phenylene,naphthalene-2,6-diyl, tetrahydronaphthalene-2,6-diyl, fluorene-2,7-diylor bicyclo[2.2.2]octane-1,4-diyl; in these rings, optional —CH₂— may besubstituted with —O—, optional —CH═ may be substituted with —N═, andoptional hydrogen may be substituted with halogen, alkyl having a carbonnumber of approximately 1 to approximately 5 or halogenated alkyl havinga carbon number of approximately 1 to approximately 5; Z isindependently a single bond or alkylene having a carbon number ofapproximately 1 to approximately 20; in the alkylene, optional —CH₂— maybe substituted with —O—, —CO—, —COO—, —OCO—, —CH═CH—, —CF═CF— or —C≡C—,and optional hydrogen may be substituted with halogen; Y is a singlebond or alkylene having a carbon number of approximately 1 toapproximately 20; in the alkylene, optional —CH₂— may be substitutedwith —O—, —CO—, —COO—, —OCO— or —CH═CH—, and optional hydrogen may besubstituted with halogen; and m and n are each an integer ofapproximately 0 to approximately 5, wherein m and n are not 0 at thesame time.
 2. The compound of claim 1, wherein in Formula (1), m+n is aninteger of 1 to
 3. 3. The compound of claim 1, wherein in Formula (1),m+n is
 2. 4. The compound of claim 1, wherein in Formula (1), R^(a) isindependently alkyl having a carbon number of approximately 1 toapproximately 10, alkoxy having a carbon number of approximately 1 toapproximately 10 or alkenyl having a carbon number of approximately 2 toapproximately 10, and of which optional hydrogens thereof may besubstituted with fluorine; A is independently 1,4-cyclohexylene,1,4-phenylene, pyridine-2,5-diyl, pyridazine-3,6-diyl orpyrimidine-2,5-diyl, and optional hydrogens thereof may be substitutedwith chlorine, fluorine, alkyl having a carbon number of approximately 1to approximately 3 or fluoroalkyl having a carbon number ofapproximately 1 to approximately 3; Z is independently a single bond,—CH₂O—, —OCH₂—, —COO—, —OCO—, —CH═CH—, —(CH₂)₂COO—, —OCO(CH₂)₂—,—CH═CH—COO—, —OCO—CH═CH— or —C≡C—; Y is a single bond or alkylene havinga carbon number of approximately 1 to approximately 10; in the alkylene,optional —CH₂— may be substituted with —O—, —COO— or —OCO—.
 5. Acompound represented by any of Formulas (I), (II) and (III):

wherein in Formulas (I), (II) and R^(a) is independently halogen, cyano,—CF₃, —CF₂H, —CFH₂, —OCF₃, —OCF₂H, —N═C═O, —N═C═S or alkyl having acarbon number of approximately 1 to approximately 20; in the alkyl,optional —CH₂— may be substituted with —O—, —S—, —SO₂—, —CO—, —COO—,—OCO—, —CH═CH—, —CF═CF— or —C≡C—, and optional hydrogen may besubstituted with halogen; R^(b) is fluorine or —CF₃; A is independently1,4-cyclohexylene, 1,4-cyclohexenylene, 1,4-phenylene,naphthalene-2,6-diyl, tetrahydronaphthalene-2,6-diyl, fluorene-2,7-diylor bicyclo[2.2.2]octane-1,4-diyl; in these rings, optional —CH₂— may besubstituted with —O—, optional —CH═ may be substituted with —N═; andoptional hydrogen may be substituted with halogen, alkyl having a carbonnumber of approximately 1 to approximately 5 or halogenated alkyl havinga carbon number of approximately 1 to approximately 5; Z isindependently a single bond or alkylene having a carbon number ofapproximately 1 to approximately 20; in the alkylene, optional —CH₂— maybe substituted with —O—, —CO—, —COO—, —OCO—, —CH═CH—, —CF═CF— or —C≡C—,and optional hydrogen may be substituted with halogen; and Y is a singlebond or alkylene having a carbon number of approximately 1 toapproximately 20; in the alkylene, optional —CH₂— may be substitutedwith —O—, —CO—, —COO—, —OCO— or —CH═CH—, and optional hydrogen may besubstituted with halogen.
 6. The compound of claim 5, wherein inFormulas (I), (II) and (III)), R^(a) is independently alkyl having acarbon number of approximately 1 to approximately 10, alkoxy having acarbon number of approximately 1 to approximately 10 or alkenyl having acarbon number of approximately 2 to approximately 10, and of whichoptional hydrogens thereof may be substituted with fluorine; A isindependently 1,4-cyclohexylene, 1,4-phenylene, pyridine-2,5-diyl,pyridazine-3,6-diyl or pyrimidine-2,5-diyl, and of which optionalhydrogens thereof may be substituted with chlorine, fluorine, alkylhaving a carbon number of approximately 1 to approximately 3 orfluoroalkyl having a carbon number of approximately 1 to approximately3; Z is independently a single bond, —CH₂O—, —OCH₂—, —COO—, —OCO—,—CH═CH—, —(CH₂)₂COO—, —OCO(CH₂)₂—, —CH═CH—COO—, —OCO—CH═CH— or —C≡C—; Yis a single bond or alkylene having a carbon number of approximately 1to approximately 10; in the alkylene, optional —CH₂— may be substitutedwith —O—, —COO— or —OCO—.
 7. The compound of claim 5, wherein inFormulas (I), (II) and (III), R^(a) is independently alkyl having acarbon number of approximately 1 to approximately 10 or alkoxy having acarbon number of approximately 1 to approximately 10; A is independently1,4-cyclohexylene or 1,4-phenylene; Z is independently a single bond,—COO—, —OCO—, —CH═CH—, —(CH₂)₂COO—, —OCO(CH₂)₂—, —CH═CH—COO—,—OCO—CH═CH— or —C≡C—; Y is a single bond or alkylene having a carbonnumber of approximately 1 to approximately 10; in the alkylene, —CH₂—adjacent to the ring may be substituted with —O—, —COO— or —OCO—.
 8. Acomposition comprising at least one compound of claim
 1. 9. Thecomposition of claim 8, further comprising a polymerizable compoundwhich is different from the compound of claim
 1. 10. The composition ofclaim 8, further comprising a polymerizable optically active compoundwhich is different from the compound of claim
 1. 11. The composition ofclaim 8, further comprising a non-polymerizable liquid crystallinecompound.
 12. The composition of claim 8, further comprising anon-polymerizable optically active compound.
 13. The composition ofclaim 8, further comprising a polymerization initiator.
 14. Thecomposition of claim 8, further comprising a solvent.